Method of forming high aspect ratio features

ABSTRACT

Methods and systems for forming high aspect ratio features on a substrate are disclosed. Exemplary methods include forming a first carbon layer within a recess, etching a portion of the first carbon layer within the recess, and forming a second carbon layer within the recess. Structures formed using the methods or systems are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of and priority to U.S. Provisional Application No. 62/962,035, filed on Jan. 16, 2020 in the United States Patent and Trademark Office, the disclosure of which is incorporated herein in its entirety by reference.

FIELD OF INVENTION

The present disclosure generally relates to methods of forming structures suitable for use in the manufacture of electronic devices. More particularly, examples of the disclosure relate to methods of forming a structure including high aspect ratio features using carbon-containing materials.

BACKGROUND OF THE DISCLOSURE

During the manufacture of devices, such as semiconductor devices, it is often desirable to form structures having high aspect ratio features (e.g., high aspect ratio trenches or gaps). Some techniques to form features include patterning, etching, and masking layer removal. In some cases, features having aspect ratios of greater than 50 or even 60 may be achieved.

Etching of silicon-containing materials can be used for formation of various features. A comparative process 500 of forming a feature is depicted in FIG. 5, wherein FIG. 5(a) depicts the result of step S502 of providing an intermediate structure 522 having a masking layer 532 deposited thereon. The intermediate structure 522 comprises a substrate 524 comprising one or more (e.g., a plurality of) layers 526 deposited thereon. The masking layer 532 overlies the top most layer 530 of the one or more layers 526. The one or more layers 526 may comprise, e.g., alternating layers. As depicted in FIG. 5, the one or more layers 526 may comprise one or more silicon dioxide (SiO₂) layer(s) 560 alternating with one or more silicon nitride (SiN) layer(s) 528; however, other configurations are possible, including a single layer or layers comprising other materials. Top most layer 530 may be a layer of SiO₂, SiN, or other material.

As depicted in FIG. 5(b), after a patterning step S504, the masking layer 532 has an unmasked opening 534 therein. As depicted in FIG. 5(c), after etching followed by masking layer 532 removal in step S506, a feature 536 is formed in the intermediate structure 522 to form intermediate structure 523. As depicted in FIG. 5(d), after a step of carbon filling S508, a carbon-containing material 538 covers the surface of the intermediate structure 523 and is within the feature 536. As depicted in FIG. 5(e), after a step of carbon etching S510, the feature 536 is filled with a remaining portion of carbon-containing material 540. The remaining portion of carbon-containing material 540 protects the feature 536 from filling with unwanted material during subsequent steps. As depicted in FIG. 5(f), after a step of deposition S512 of one or more additional layer(s) 542 having a top layer 544 to produce the intermediate structure 582, the feature 536 remains filled with the remaining portion of the carbon-containing material 540, thereby protecting the feature 536 from filling with the material deposited in additional layer deposition step S512 and can protect the integrity of intermediate structure 582. As noted above, the one or more additional layer(s) 542 may comprise one or more SiO₂ layer(s) 584 optionally alternating with one or more SiN layer(s) 582. As depicted in FIG. 5(g), after a step of masking layer deposition S514, a masking layer 546 is on a surface of the top layer 544 of the one or more additional layer(s) 542. As depicted in FIG. 5(h), after a step of patterning S516, an opening 548 appears in the masking layer 546. As depicted in FIG. 5(i), after a step of etching the additional layers S518, there is an opening 550 above the remaining portion of carbon-containing material 540 in the feature 536. And, as depicted in FIG. 5(j), after a step of masking layer and carbon layer removal S520, there is a (feature) recess 552, which comprises the feature 536 and the opening 550 formed in etching steps S506 and S518, respectively.

While the process depicted in FIG. 5 can be effective in forming various features, there are remaining problems, including poor filling of the recess, resulting in bowing, and low throughput, as illustrated in FIGS. 6 and 7. In FIG. 6, an example of poor filling is shown. As depicted in FIG. 6, a structure 602 having one or more (e.g., a plurality of) layers 606 on a substrate 604 has deposited thereon a carbon-containing material 612. The one or more layers 606 may comprise, e.g., alternating SiO₂ layer(s) 610 and/or SiN layer(s) 608, although other configurations are possible. Atop layer 620 of the one or more layers 606 has a surface underlying the carbon-containing material 612. The carbon-containing material 612 may fail to adequately fill the recess 614, resulting in bottleneck formation where the carbon-containing material fails to cover an opening of the recess 614 after partial removal of the carbon layer back to a top surface of the surface of top layer 620. Bottlenecks can cause over etching and/or bowing during later etching steps.

As depicted in FIG. 7, a structure 702 has one or more (e.g., a plurality of) layers 706 formed on a substrate 704. The one or more (e.g., plurality of) layers 706 may comprise alternating SiO₂ layer(s) 710 and/or SiN layer(s) 708, although other configurations are possible. As depicted in FIG. 7(a), a carbon containing layer 712 covers the structure 702 and is within a recess 714. As depicted in FIG. 7(b), structure 702 has a height h. As the height h increases, the time required to deposit the carbon containing material and/or the time to remove the carbon containing layer 712 increase, resulting in poor throughput. Thus, complete filling of the recess 714 may avoid over etching, but may also result in poor output, as high aspect ratio features may require long periods of carbon deposition and/or removal to completely remove carbon layers from a recess.

Any discussion, including discussion of problems and solutions, set forth in this section, has been included in this disclosure solely for the purpose of providing a context for the present disclosure, and should not be taken as an admission that any or all of the discussion was known at the time the invention was made or otherwise constitutes prior art.

SUMMARY OF THE DISCLOSURE

Various embodiments of the present disclosure relate to methods of fabricating structures having high aspect ratio features suitable for use in the formation of electronic devices. While the ways in which various embodiments of the present disclosure address drawbacks of prior methods and structures are discussed in more detail below, in general, exemplary embodiments of the disclosure provide improved methods for forming features on a surface of a substrate with carbon-containing materials and/or to forming layers or structures comprising carbon. Exemplary methods can prevent or mitigate bowing during formation of the structures and/or can exhibit relatively high throughput, e.g., by reducing carbon deposition and/or etch times.

In accordance with various embodiments of the disclosure, methods of fabricating structures (e.g., structures including one or more high aspect ratio features) are provided. Exemplary methods can include providing a substrate in a reaction chamber of a reactor, the substrate comprising one or more layers comprising a surface and a recess formed within the one or more layers; forming a first carbon layer on the surface, thereby partially filling the recess, (wherein the first carbon layer can be initially flowable), partially removing a portion of the first carbon layer within the recess; and forming a second carbon layer overlying a remaining portion of the first carbon layer. The second carbon layer can also be initially flowable. The initial flowability of the first carbon layer may be greater than the initial flowability of the second carbon layer. In some exemplary methods, the step of etching a portion of the first carbon layer can include etching the first carbon layer until a surface of the first carbon layer within the recess is below the top of the recess. Exemplary methods can further include a step of partially removing (e.g., etching) the second carbon layer, wherein a remaining portion of the second carbon layer is coplanar or substantially coplanar with an opening of the recess; depositing at least one additional layer overlying the remaining portion of the second carbon layer; etching the at least one additional layer to form an opening to the remaining portion of the second carbon layer, and removing the remaining portion of the second carbon layer and the remaining portion of a first carbon layer, thereby forming a high aspect ratio feature. In some cases, the first carbon layer can have a top surface that can initially extend to (e.g., be coplanar or substantially coplanar with) at least a top surface of the recess. In accordance with further examples of the disclosure, the second carbon layer can fill the recess to at least a top surface of the substrate. The step of etching a portion of the second carbon layer can also include etching the second carbon layer until a surface of the second carbon layer within the recess is coplanar or substantially coplanar with a surface defining a recess opening. Exemplary methods can comprise treatment, which can include plasma treatment—e.g., treatment with species formed from one or more of argon, helium, nitrogen, and hydrogen. The treatment, e.g., plasma treatment, may be part of first and/or second carbon layer formation steps. Various etching steps can be performed using one or more steps of plasma etching, e.g., one or more plasma-enhanced etch processes.

In accordance with yet further exemplary embodiments of the disclosure, a structure is formed, at least in part, according to a method described herein.

In accordance with yet further exemplary embodiments of the disclosure, a system is provided for performing a method and/or for forming a structure as described herein.

These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of certain embodiments having reference to the attached figures; the invention not being limited to any particular embodiment(s) disclosed.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

A more complete understanding of exemplary embodiments of the present disclosure can be derived by referring to the detailed description and claims when considered in connection with the following illustrative figures.

FIG. 1 illustrates a method (process) of fabricating a structure including a high aspect ratio feature according to embodiments of the present disclosure.

FIG. 2 schematically illustrates a structure having a feature with a vertically aligned sidewall in accordance with exemplary embodiments of the present disclosure.

FIG. 3 schematically illustrates a structure having a feature with a substantially vertically aligned sidewall with a lip.

FIG. 4 schematically illustrates a structure having a vertically aligned sidewall with an overhang.

FIG. 5 illustrates a comparative process of forming a feature in a structure using a single carbon-containing material.

FIG. 6 illustrates incomplete filling of a recess with a carbon-containing material.

FIG. 7 illustrates a high aspect ratio feature filled with a carbon-containing material.

FIG. 8 illustrates a system in accordance with exemplary embodiments of the disclosure.

It will be appreciated that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of illustrated embodiments of the present disclosure.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

Although certain embodiments and examples are disclosed below, it will be understood by those in the art that the invention extends beyond the specifically disclosed embodiments and/or uses of the invention and obvious modifications and equivalents thereof. Thus, it is intended that the scope of the invention disclosed should not be limited by the particular disclosed embodiments described below.

The present disclosure generally relates to methods of depositing materials, to methods of forming structures and features, to structures and features formed using the methods, and to systems for performing the methods and/or forming the structures and/or features. By way of examples, the methods described herein can be used to form structures including features, such as recesses or gaps (e.g., trenches or vias). Formation of features may include masking or blocking (e.g., at least partially filling) an existing feature, such as a recess, with material, such as carbon-containing (e.g., organic) material to form a base upon which additional layers can be deposited. The terms gap and recess, as used herein, can be used interchangeably.

Incomplete (partial) filling of a recess with a carbon-containing material can lead to formation of a void. Embodiments disclosed herein take advantage of void formation to provide an effective carbon base, thereby permitting efficient formation of structures including high aspect ratio features, such as recesses. In some embodiments disclosed herein, features including an aspect ratio of, e.g., 60 to 70, may be formed. In some embodiments, high throughput may be achieved. In some embodiments, bowing and/or over-etching may be mitigated or even avoided.

In this disclosure, “gas” can refer to material that is a gas at normal temperature and pressure, a vaporized solid and/or a vaporized liquid, and may be constituted by a single gas or a mixture of gases, depending on the context. A gas other than a process gas, i.e., a gas introduced without passing through a gas distribution assembly, such as a showerhead, other gas distribution device, or the like, may be used for, e.g., sealing a reaction chamber, which includes a seal gas, such as a rare gas. In some cases, such as in the context of deposition of material, the term “precursor” can refer to a compound that participates in the chemical reaction that produces another compound, and particularly to a compound that constitutes a film matrix or a main skeleton of a film, whereas the term “reactant” can refer to a compound, in some cases other than a precursor, that activates a precursor, modifies a precursor, or catalyzes a reaction of a precursor; a reactant may provide an element (such as O, H, N, C) to a film matrix and become a part of the film matrix when, for example, radio frequency (RF) power is applied. In some cases, the terms precursor and reactant can be used interchangeably. The term “inert gas” refers to a gas that does not take part in a chemical reaction to an appreciable extent and/or a gas that excites a precursor when, for example, RF power is applied, but unlike a reactant, it may not become a part of a film matrix to an appreciable extent.

As used herein, the term “substrate” can refer to any underlying material or materials that may be used to form, or upon which, a device, a circuit, or a film may be formed. A substrate can include a bulk material, such as silicon (e.g., single-crystal silicon), other Group IV materials, such as germanium, or compound semiconductor materials, such as GaAs, and can include one or more layers overlying or underlying the bulk material. Further, the substrate can include various features, such as gaps (e.g., recesses or vias), lines or protrusions, such as lines having gaps formed therebetween, and the like formed within or on at least a portion of a layer or bulk material of the substrate. By way of examples, one or more features can have a width of about 100 nm to about 200 nm, a depth or height of about 5,000 nm to about 15,000 nm, and/or an aspect ratio of about 25 to about 150. By way of further examples, a substrate can include a bulk material and one or more layers of, e.g., silicon oxide and silicon nitride overlying the bulk material. The one or more layers can include a recess and a surface.

In some embodiments, “film” refers to a layer extending in a direction perpendicular to a thickness direction. In some embodiments, “layer” refers to a material having a certain thickness formed on a surface and can be a synonym of a film or a non-film structure. A film or layer may be constituted by a discrete single film or layer having certain characteristics or multiple films or layers, and a boundary between adjacent films or layers may or may not be clear and may or may not be established based on physical, chemical, and/or any other characteristics, formation processes or sequence, and/or functions or purposes of the adjacent films or layers. The layer or film can be continuous—or not.

As used herein, the term “carbon layer” or “carbon-containing material” can refer to a layer or material whose chemical formula can be represented as including carbon. Layers comprising carbon-containing material can include other elements, such as one or more of nitrogen and hydrogen.

As used herein, the term “structure” can refer to a partially or completely fabricated device structure. By way of examples, a structure can include a substrate with one or more layers and/or features formed thereon.

Plasma-enhanced chemical vapor deposition (PECVD) can refer to a process used to deposit thin films from a gas state (vapor) to a solid state on a substrate. Chemical reactions are involved in the process, which occur after creation of a plasma of the reactive gases. The plasma can be applied to the space filled with the reactive and/or inert gases. In some embodiments, a radio frequency (RF) plasma source is employed to create the plasma, though any type of plasma source capable of generating a direct and/or remote plasma may be employed, including microwave and DC sources. In some embodiments, a remotely-generated plasma may be employed to supply reactive species. In further embodiments (e.g., pulse PECVD) only one of the reactants, either a precursor or the reactive species may be provided continuously to the chamber while the other reactant is pulsed intermittently.

In this disclosure, “continuously” refers to without breaking a vacuum, without interruption as a timeline, without any material intervening step, without changing treatment conditions, immediately thereafter, as a next step, or without an intervening discrete physical or chemical structure between two structures other than the two structures in some embodiments and depending on the context.

A flowability (e.g., an initial flowability) can be determined as follows:

TABLE 1 bottom/top ratio (B/T) Flowability  0 < B/T < 1 None  1 ≤ B/T < 1.5 Poor 1.5 ≤ B/T < 2.5 Good 2.5 ≤ B/T < 3.5 Very good 3.5 ≤ B/T Extremely good where B/T refers to a ratio of thickness of film deposited at a bottom of a recess to thickness of film deposited on a top surface where the recess is formed, before the recess is filled or partially filled. Typically, the flowability is evaluated using a wide recess having an aspect ratio of about 1 or less, since generally, the higher the aspect ratio of the recess, the higher the B/T ratio becomes. The B/T ratio can become higher when the aspect ratio of the recess is higher. As used herein, a “flowable” film or material exhibits good or better flowability.

As set forth in more detail below, flowability of film can be temporarily obtained when a volatile hydrocarbon precursor, for example, is polymerized by a plasma and deposited on a surface of a substrate, wherein the gaseous precursor is activated or fragmented by energy provided by plasma gas discharge, so as to initiate polymerization, and when the resultant polymer material is deposited on the surface of the substrate, the material shows temporarily flowable behavior. In some cases, when the deposition step is complete, the flowable film is no longer flowable (or exhibits reduced flowability) and solidifies, and thus, a separate solidification process may not be employed.

In this disclosure, any two numbers of a variable can constitute a workable range of the variable, and any ranges indicated may include or exclude the endpoints. Additionally, any values of variables indicated (regardless of whether they are indicated with “about” or not) may refer to precise values or approximate values and include equivalents, and may refer to average, median, representative, majority, etc. in some embodiments. Further, in this disclosure, the terms “including,” “constituted by” and “having” can refer independently to “typically or broadly comprising,” “comprising,” “consisting essentially of,” or “consisting of” in some embodiments. In this disclosure, any defined meanings do not necessarily exclude ordinary and customary meanings in some embodiments.

Turning now to the figures, FIG. 1 illustrates a method 100 of forming a structure including high aspect ratio features using two or more carbon containing layers. During step S102, a first intermediate structure 122 comprising a substrate 124 is provided into a reaction chamber of a reactor.

As depicted in FIG. 1(a), during step S102, there is provided in a reaction chamber of a reactor the first intermediate structure 122, having the substrate 124. The first intermediate structure 122 comprises a first one or more (e.g., a plurality of) layers 126, having formed therein a recess 138. The first one or more (e.g., plurality of) layers 126 may comprise, e.g., one or more alternating layers. By way of illustration, the first one or more layers 126 may comprise one or more silicon oxide layer(s) 128 alternating with one or more silicon nitride layer(s) 130. Other configurations are possible. The first one or more layers 126 (e.g., silicon oxide and/or silicon nitride layers) may be deposited by any suitable process, such as CVD, PECVD, or PEALD. Although illustrated with reference to a plurality of layers 126, the first intermediate structure 122 could include a single layer of material in place of a plurality of layers 126. Although illustrated with silicon oxide and/or silicon nitride as layer materials, other materials may be used. The first intermediate structure 122 can become a substrate for subsequent steps.

The first intermediate structure 122 has a first top layer 132. Recess 138 can be formed in the first one or more layers 126, e.g., using techniques described above, such as masking, patterning, and etching techniques. The recess 138 has a recess sidewall 134 and an opening 136. In some embodiments, a recess sidewall 134 may be vertical or substantially vertical. In some embodiments, the opening 136 is co-planar or substantially co-planar with a surface of the first top layer 132 of the first one or more (e.g., plurality of) layers 126.

As depicted in FIG. 1(b), after a first step of depositing a carbon-containing material S104, the first intermediate structure 122 has deposited on the first top layer 132 a first carbon-containing material 140, which has a flowability such that it partially fills the recess 138 to form a void 142 beneath a portion of the first carbon-containing material 140 within the recess 138. Exemplary techniques for depositing first carbon-containing material 140 on the first intermediate structure 122 during step S104 include PECVD techniques.

A PECVD technique used during the step of depositing the first carbon-containing material 140, may include introduction of a suitable precursor to a reaction chamber while applying RF power to form a plasma within the reaction chamber. A frequency of the RF power may be in a range of about 2.0 MHz to about 27.12 MHz, with a power of about 50 W to about 300 W. In some embodiments a direct current (DC) or RF bias may be applied, e.g., through electrodes, such as one or more of a susceptor and/or a gas distribution device. In some such cases, an RF frequency may be applied on a susceptor stage/susceptor during at least a portion of step S104. The RF frequency applied to the susceptor stage/susceptor during step S104 can range from about 400 kHz to about 800 kHz. One or more inert gases may be introduced into the reaction chamber during the step of depositing the first carbon-containing material 140. The one or more inert gases may include argon, helium, nitrogen and/or hydrogen.

As mentioned above, during step S104, a precursor may be introduced to a reaction chamber. Suitable precursors may be represented by the formula C_(x)H_(y)N_(z), where x can be a natural number greater than or equal to 2, y can be a natural number, and z can be zero or a natural number. For example, x can range from about 2 to about 15, y can range from about 4 to about 30, and z can range from about 0 to about 10. Additionally, or alternatively, the precursor can include a chain or cyclic molecule having two or more carbon atoms and one or more hydrogen atoms, such as molecules represented by the formula C_(x)H_(y)N_(z). By way of particular examples, the precursor can be, or include, one or more of double bonding, and/or one or more aromatic hydrocarbon structures.

In some embodiments, the first carbon containing material 140 may have high flowability and low etching selectivity. Etching selectivity refers to the ratio of etching rate of one material relative to other materials. In some embodiments, an etching selectivity of the carbon containing material 140 relative to materials in the first one or more (e.g., plurality of) layers 126 is low, e.g., less than 2.0. An initial flowability of first carbon containing material 140 can be greater than ‘Extremely good’ as defined in Table 1.

In addition to depositing the first carbon-containing material 140, step S104 may optionally comprise a treatment step. In some embodiments, step S104 may comprise no plasma treatment or weak plasma treatment. Weak plasma treatment may comprise contacting the first carbon-containing material with an inert gas, such as one or more of argon, helium, nitrogen, and/or hydrogen while applying RF power to form excited species from the one or more of argon, helium, nitrogen, and/or hydrogen. In some embodiments, weak plasma treatment during step S104 may include exposure of the first intermediate structure 122 to a plasma having a (e.g., continuous) RF power of from about 50 W to about 300 W. An RF frequency used during step S104 may be from about 2.0 MHz to about 27.12 MHz. In some embodiments, exposure of first carbon-containing material 140 to the plasma during the treatment step of step S104 may range from about 1 to 10 seconds, e.g., from about 1.0 to about 10.0 seconds. (Seconds may be abbreviated herein as “sec.”) During step S104, a temperature in the reaction chamber may be less than 100° C.

As depicted in FIG. 1(c), after a first step of partial carbon-layer removal S106, a remaining portion of the first carbon-containing material 144 remains in the recess 138. A void 142 can be formed beneath the remaining portion of the first carbon-containing material 144. Thus, the remaining portion of the first carbon-containing material 144 forms a void 142 within recess 138. In some embodiments, a portion of the recess 138 above the remaining portion of the first carbon-containing material 144 may remain open after the first partial carbon-layer removal step S106. Plasma etching may be used for partial carbon-layer removal during step S106. During step S106, an etchant may be flowed to the reaction chamber. Exemplary etchants include oxygen-containing gases, such as oxygen (O₂), or N₂O, or hydrogen-containing gases, such as hydrogen (H₂), or NH₃. A plasma may produce oxygen and/or hydrogen containing active species during step S106. In some cases, the gas employed during step S106 may include from about 5.0% to about 50.0% oxygen-containing gas and/or hydrogen-containing gas in an inert gas, such as helium, argon or the like. A flowrate of the gas (e.g., oxygen-containing gas, hydrogen-containing gas, and/or any inert gas) during step S106 can range from about 1.0 slm to about 4.0 slm.

Activated species can be formed from the gas (e.g., oxygen-containing gas, hydrogen-containing gas, and/or any inert gas) during step S106 using a direct and/or remote plasma. A power applied to electrodes during step S106 can range from about 50 W to about 400 W. A frequency of the power applied during step S106 can range from about 2.0 MHz to about 27.12 MHz.

As depicted in FIG. 1(d), after a second step S108 comprising depositing a second carbon-containing material 146, the recess 138 is partially filled with a second carbon-containing material 146, which can be deposited on a surface 176 of the top layer 132 of the first one or more (e.g., plurality of) layers 126. Exemplary techniques for depositing second carbon-containing material 146 on the top layer 132 of the first one or more (e.g., plurality of) layers 126 during step S108 include PECVD techniques. A PECVD technique used during the step of depositing the second carbon-containing material 146, may include introduction of a suitable precursor to a reaction chamber while applying RF power to form a plasma within the reaction chamber. A frequency of the RF power may be in a range of about 2.0 MHz to about 27.12 MHz, with a power of about 50 W to about 300 W. In some embodiments a direct current (DC) or RF bias may be applied, e.g., through electrodes, such as one or more of a susceptor and/or a gas distribution device. In some such cases, an RF frequency may be applied on a susceptor stage/susceptor during at least a portion of step S108. The RF frequency applied to the susceptor stage/susceptor during step S108 can range from about 400 kHz to about 800 kHz. In some embodiments, a film density of a carbon layer may be adjusted, controlled, or manipulated by manipulating one or more of a radio frequency (RF) power, an exposure time to a plasma, or a bias RF power, e.g., as applied to a susceptor stage/susceptor.

One or more inert gases may be introduced into the reaction chamber during the step S108 of depositing the second carbon-containing material 146. The one or more inert gases may include argon, helium, nitrogen and/or hydrogen.

During step S108, a precursor may be introduced to a reaction chamber. Suitable precursors for depositing second carbon-containing material 146, which may be the same or different from those used in depositing the first carbon-containing material 140, may be represented by the formula C_(x)H_(y)N_(z), where x can be a natural number greater than or equal to 2, y can be a natural number, and z can be zero or a natural number. For example, x can range from about 2 to about 15, y can range from about 4 to about 30, and z can range from about 0 to about 10. Additionally, or alternatively, the precursor can include a chain or cyclic molecule having two or more carbon atoms and one or more hydrogen atoms, such as molecules represented by the formula C_(x)H_(y)N_(z). By way of particular examples, the precursor can be or include one or more of double bonding, and/or one or more aromatic hydrocarbon structures.

In some embodiments, the second carbon-containing material 146 may have lower flowability and/or higher etching selectivity compared to first carbon-containing material 140. Etching selectivity refers to the ratio of etching rate of one material relative to other materials. In some embodiments, an etching selectivity of the second carbon-containing material 146 relative to materials in the one or more (e.g., plurality of) additional layers 152 (see description of FIG. 1(f), infra) is relatively high, e.g., greater than 2.0. An initial flowability of carbon containing material 146 can be less than ‘Good’ as defined in Table 1.

In some embodiments, after depositing the second carbon-containing material 146, step S108 also may also comprise a plasma treatment step. In some embodiments, a treatment step may comprise strong plasma treatment. Continuous radio frequency (RF) may be used during step S108. Strong plasma treatment may comprise contacting the second carbon-containing material 146 with activated species formed from an inert gas, such as one or more of argon, helium, nitrogen, and/or hydrogen by exposing the gas to a plasma. In some exemplary embodiments, a strong plasma treatment during step S108 may include exposure of the second carbon-containing material 146 to a plasma having a (e.g., continuous) RF power of from about 50 W to about 300 W. An RF frequency used during step S108 may be from about 2.0 MHz to about 27.12 MHz. In some embodiments, exposure of second carbon-containing material 146 to the plasma during the treatment step of step S108 may range from about 5 to 30 seconds, e.g., from about 5.0 to about 30.0 seconds. (Seconds may be abbreviated herein as “sec.”) During step S108, a temperature in the reaction chamber may be less than 100° C.

As depicted in FIG. 1(e), after a step S110 of partial removal of the second carbon-containing material 146, a remaining portion of the second carbon-containing material 148 having a surface 150 remains in the recess 138, and first top layer 132 has first top surface 176. Plasma etching may be used during partial removal of the second carbon-containing material during step S110. During step S110, an etchant may be flowed to the reaction chamber. Exemplary etchants used in step S110 may include oxygen-containing gases, such as oxygen (O₂), and hydrogen-containing gases, such as hydrogen (H₂). In some such cases, the gas used in step S110 may include from about 5.0% to about 50.0% oxygen-containing gas and/or hydrogen-containing gas in an inert gas, such as helium, argon or the like. A flowrate of the gas (e.g., oxygen-containing gas, hydrogen-containing gas, and/or any inert gas) in step S110 can range from about 1.0 slm to about 4.0 slm.

Activated species can be formed from the gas (e.g., oxygen-containing gas, hydrogen-containing gas, and/or any inert gas) using a direct and/or remote plasma in step S110. A power applied to electrodes during step S110 can range from about 100 W to about 800 W. A frequency of the power used in step S110 can range from about 2.0 MHz to about 27.12 MHz.

In some embodiments, the surface 150 of the remaining portion of the second carbon-containing material 148 remaining in the recess 138 after S110 is co-planar or substantially co-planar with a first top surface 176 of the first top layer 132 of the first one or more (e.g., plurality of) layers 126. In some embodiments, the remaining portion of the second carbon-containing material 148 within recess 138 after step S110 is such that the portion of the remaining portion of the first carbon containing material 144 and the remaining portion of the second carbon layer 148 block depositing of materials within the recess 138 and void 142 during later process steps, e.g., by way of illustration, steps S112-S118.

As used herein “coplanar” means that a surface of one feature (e.g., a second carbon layer) is coplanar with a surface of another feature (e.g., a structure), within the limits of conventional methods of measurement, such as cross-sectional TEM or SEM. As used herein, “substantially coplanar” means that a surface of a first feature is no more than five percent (5%) higher or lower than a surface of a second (reference) feature, wherein a difference in height between the two surfaces is the numerator, and a thickness of the thinner of the two features is the denominator. In some embodiments, the surface 150 of the remaining portion of the second carbon containing material 148 formed in step S110 is “substantially coplanar” with the first top surface 176 of first top layer 132, meaning that it may be up to 5%, 4%, 3%, 2%, 1%, 0.5%, 0.25%, 0.1%, 0.05%, or 0.01% higher or lower than the first top surface 176 (wherein the first top layer 132 is the reference layer whose width is the denominator, when first top layer 132 is thinner than the remaining portion of the second carbon-containing material 148).

As depicted in FIG. 1(f), after a step S112 of depositing additional layer(s) 152 on the first top layer 132 of the first one or more (e.g., plurality of) layers 126 and the surface 150 of the remaining portion of the second carbon-containing material 148, one or more (e.g., a plurality of) additional layers 152 are formed, thereby forming second intermediate structure 182. The one or more additional layers 152 formed in step S112 have a top layer 154 having a surface 156. As depicted in FIG. 1(f), after a step of deposition S112 of one or more additional layer(s) 152, the remaining portion of the first carbon-containing material 144 and the remaining portion of the second carbon-containing material 148 remain in recess 138, the void 142 remaining underneath the remaining portion of the first carbon-containing material 144, thereby protecting the recess 138 from filling with the material deposited in additional layer deposition step S112. The one or more additional layers 152 may be formed by an any suitable process, such as CVD, PECVD, or PEALD.

As depicted in FIG. 1(g), after a step of masking layer deposition S114, a masking layer 158 is formed on the surface 156 of top layer 154. Suitable masking layer materials may comprise SiC, metal oxide (TiO, ZrO, AlO, etc.), or an organic layer, and may be deposited by methods such as CVD, PECVD, or PEALD.

As depicted in FIG. 1(h), after a step S116 of patterning, including partial masking layer removal, there is an exposed portion 160 of the surface 156 of top layer 154 of the one or more (e.g., plurality of) additional layers 152. Patterning may be carried out by suitable methods, such as lithography.

As depicted in FIG. 1(i), after a step of etching S118, an opening 162 is formed in the one or more (e.g., plurality of) additional layers 152. The opening 162 has an opening sidewall 164. Step S118 can include the same or similar techniques described above in connection with step S102.

As depicted in FIG. 1(j), after a step of masking layer and carbon layer removal S120, a feature 166 is formed. The feature 166 formed in step S120 has a feature sidewall 170. The feature 166 comprises both the recess 138 and the opening 162. Thus, the second etching step S118, in combination with the removal of the carbon layers in step S120, has formed a single high aspect ratio feature 166 in the first one or more layers 126 and one or more additional layers 152, thereby forming a structure 192 having the feature 166 having a high aspect ratio. The masking layer may be removed by a suitable method, such as wet process (use of HF or H₂O₂—NH₄OH-based chemical) or dry process (plasma etching by CF-based chemical or Cl-based chemical). The remaining portion of the second carbon-containing layer 148 and the remaining portion of the first carbon-containing material 144 can be removed using techniques described above, e.g., carbon layer plasma etching as described with respect to steps S106 and/or S110.

The combination of the remaining portion of the second carbon-containing material 148 and the remaining portion of the first carbon-containing material 144 (e.g., having a void 142 below the remaining portion of the first carbon-containing material 144) together effectively block depositing of material during processing steps, e.g., steps S112, S114, S116, and S118. The combination of the remaining portion of the second carbon-containing material 148 and the remaining portion of the first carbon-containing material 144 (e.g., having a void 142 below the remaining portion of the first carbon-containing material 144) may be more easily and/or more quickly removed than a comparative carbon-containing material, such as carbon-containing material 714, depicted in FIG. 7. Thus, method 100 and related methods within the scope of the invention may achieve higher throughput than a comparative method 500. Without wishing to be bound by theory, such higher throughput may be achieved because, together the remaining portion of the first carbon-containing material 144 (e.g., having high flowability and low etching selectivity) and the portion of the remaining second carbon-containing material 148 (e.g., having lower flowability and/or higher etching selectivity compared to first carbon-containing material) are more easily and/or more quickly deposited and/or removed than a comparative carbon-containing material that comprises only one carbon-containing material and/or does not have a void 142 below the remaining portion of the first carbon-containing material 144 that facilitates void formation. Accordingly, again without being bound by theory, it is believed that methods of the invention such the method 100 depicted in FIG. 1, using two carbon-containing materials, and optionally including a void, can achieve higher throughput than comparative methods using a single carbon-containing material.

Looking now to FIGS. 2-4, a structure 222 has formed therein a feature 266. As depicted in FIG. 2, the feature 266 has a feature sidewall 270, which comprises an opening sidewall 264 and a recess sidewall 234. The opening sidewall 264 and recess sidewall 234 meet at junction 202 between a first top layer 232 of a first one or more layers 226 and a second one or more additional layers 252. The first top layer 232 of the first one or more layers 226 has a thickness w.

As depicted in FIG. 2, in some embodiments, the recess sidewall 234 and the opening sidewall 264 are in vertical alignment or substantially in vertical alignment, such that there is a seamless or substantially seamless junction 202 between the recess sidewall 234 and the opening sidewall 264.

As depicted in FIG. 3, there is a structure 322, in which the feature sidewall 270 may include a lip 372, resulting from slight misalignment of opening sidewall 264 and recess side wall 234. In such cases, there may be a lip variance v¹, which is a horizontal distance along the lip 372 between the opening sidewall 264 and recess side wall 234.

As depicted in FIG. 4, there is a structure 422, in which the feature sidewall 270 may include an overhang 474, caused by a slight misalignment of opening sidewall 264 and recess side wall 234. In such cases, there may be an overhang variance v¹¹, which is a horizontal distance along the overhang between the opening sidewall 264 and the recess side wall 234.

Although FIG. 3 illustrates a lip 272 and FIG. 4 illustrates an overhang 474, it will be understood that a structure 322, 422 may, in case of a slight misalignment, have both a lip 272 and an overhang 474, and thus may have both a lip variance v¹ and an overhang variance v¹¹.

As used herein “in vertical alignment” means that there is no lip or overhang measurable by conventional methods (e.g., CVD or ALD) in the feature sidewall 270; and “substantially in vertical alignment” means that lip variance v¹ and/or overhang variance v¹¹, when measurable by conventional methods, are less than about 3% of thickness w of a first top layer 232 of the first one or more layers 226. In some embodiments, lip variance v¹ and/or overhang variance v¹¹, when measurable by convention methods, may be less than about 3% of thickness w of first top layer 232.

As used herein, “seamless” means that there is no lip or overhang measurable by convention methods (such as PECVD or PEALD) in the feature sidewall. As used herein, “substantially seamless” means that lip variance v¹ and/or overhang variance v¹¹, when measurable by conventional methods, are less than about 5% of thickness w of a first top layer 232 of the first one or more layers 226. In some embodiments, lip variance v¹ and/or overhang variance v¹¹ may be less than about 3%, of thickness w of first top layer 232.

The structure 192 illustrated in FIG. 1(j) and the structures 222, 322, 422 illustrated in FIGS. 2-4, respectively, can serve as a substrates in subsequent processing, including repeating the method illustrated in FIG. 1.

The method 100 depicted in FIG. 1 may be carried out in a reactor system 600, as depicted in FIG. 6, which can be used to perform one or more steps or sub steps as described herein and/or to form one or more structures or portions thereof as described herein.

FIG. 6 illustrates a reactor system 600 in accordance with exemplary embodiments of the disclosure. Reactor system 600 can be used to perform one or more steps or sub steps as described herein and/or to form one or more structures or portions thereof as described herein.

Reactor system 600 includes a pair of electrically conductive flat-plate electrodes 4, 2 in parallel and facing each other in the interior 11 (reaction zone) of a reaction chamber 3. A plasma can be excited within reaction chamber 3 by applying, for example, HRF power (e.g., 2.0 MHz to 27.12 MHz) from power source 25 to one electrode (e.g., electrode 4) and electrically grounding the other electrode (e.g., electrode 2). A temperature regulator is provided in a lower stage 2 (the lower electrode), and a temperature of a substrate 1 placed thereon can be kept at a desired temperature. Electrode 4 can serve as a gas distribution device, such as a shower plate. Reactant gas, dilution gas, if any, precursor gas, and/or etchant can be introduced into reaction chamber 3 using one or more of a gas line 20, a gas line 21, and a gas line 22, respectively, and through the gas distribution device 4. Although illustrated with three gas lines, reactor system 600 can include any suitable number of gas lines.

In reaction chamber 3, a circular duct 13 with an exhaust line 7 is provided, through which gas in the interior 11 of the reaction chamber 3 can be exhausted. Additionally, a transfer chamber 5, disposed below the reaction chamber 3, is provided with a seal gas line 24 to introduce seal gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer zone) of the transfer chamber 5, wherein a separation plate 14 for separating the reaction zone and the transfer zone is provided (a gate valve through which a wafer is transferred into or from the transfer chamber 5 is omitted from this figure). The transfer chamber is also provided with an exhaust line 6. In some embodiments, the deposition, etch and/or surface treatment steps are performed in the same reaction chamber, so that two or more (e.g., all) of the steps can be conducted without exposing the substrate to air or other oxygen-containing atmosphere.

In some embodiments, flow of a carrier gas to reaction chamber 3 can be accomplished using a flow-pass system (FPS), wherein a carrier gas line is provided with a detour line having a precursor reservoir (bottle), and the main line and the detour line are switched, wherein when only a carrier gas is intended to be fed to a reaction chamber, the detour line is closed, whereas when both the carrier gas and a precursor gas are intended to be fed to the reaction chamber, the main line is closed and the carrier gas flows through the detour line and flows out from the bottle together with the precursor gas. In this way, the carrier gas can flow into the reaction chamber, and can carry the precursor gas in pulses by switching between the main line and the detour line, without substantially fluctuating pressure of the reaction chamber.

A skilled artisan will appreciate that the apparatus includes one or more controller(s) 26 programmed or otherwise configured to cause one or more method steps as described herein to be conducted. The controller(s) are communicated with the various power sources, heating systems, pumps, robotics and gas flow controllers, or valves of the reactor, as will be appreciated by the skilled artisan.

In some embodiments, a dual chamber reactor (two sections or compartments for processing wafers disposed close to each other) can be used, wherein a reactant gas and a noble gas can be supplied through a shared line, whereas a precursor gas is supplied through unshared lines.

The example embodiments of the disclosure described above do not limit the scope of the invention, since these embodiments are merely examples of the embodiments of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the disclosure, in addition to those shown and described herein, such as alternative useful combinations of the elements described, may become apparent to those skilled in the art from the description. Such modifications and embodiments are also intended to fall within the scope of the appended claims. 

What is claimed is:
 1. A method of fabricating a structure including high aspect ratio features, the method comprising: a. providing in a reaction chamber a substrate having one or more layers comprising a surface and a recess formed within the one or more layers; b. forming a first carbon layer on the surface, thereby at least partially filling the recess; c. partially removing the first carbon layer; d. forming a second carbon layer overlying a remaining portion of the first carbon layer; e. partially removing the second carbon layer, wherein a remaining portion of the second carbon layer is substantially co-planar with an opening of the recess; f. depositing at least one additional layer overlying the remaining portion of the second carbon layer; and g. etching the at least one additional layer to form an opening to the remaining portion of the second carbon layer.
 2. The method of claim 1, wherein at least partially filling the recess comprises forming a void within the recess and below the first carbon layer.
 3. The method of claim 1, wherein an initial flowability of the first carbon layer is greater than an initial flowability of the second carbon layer.
 4. The method of claim 2, wherein, after the step of partially removing the first carbon layer, a remaining portion of the first carbon layer still keeps forming a void within the recess.
 5. The method of claim 1, wherein the step of partially removing the first carbon layer comprises removing at least some of the first carbon layer from the recess.
 6. The method of claim 1, wherein the step of forming the first carbon layer, the step of forming the second carbon layer, or both, comprise plasma-enhanced chemical vapor deposition (PECVD).
 7. The method of claim 1, wherein the step of forming a first carbon layer, the step of forming a second carbon layer, or both comprise providing a precursor represented by the formula C_(x)H_(y)N_(z), where x is a natural number greater than or equal to 2, y is a natural number, and z is zero or a natural number.
 8. The method of claim 1, wherein the step of forming a first carbon layer, the step of forming a second carbon layer, or both, comprise a step of plasma treatment.
 9. The method of claim 1, wherein the step of forming the first carbon layer, the step of forming the second carbon layer, or both, comprise manipulating a film density of the first carbon layer, a film density of the second carbon layer, or both, by controlling one or more of a radio frequency (RF) power, an exposure time to plasma, and bias RF power on a susceptor stage/susceptor.
 10. The method of claim 1, wherein RF frequency ranges from about 2.0 MHz to about 27.12 MHz, and RF bias frequency on a susceptor stage/susceptor ranges from about 400 kHz to about 800 kHz.
 11. The method of claim 1, wherein a temperature within the reaction space during one or more of the steps of forming the first carbon layer, forming the second carbon layer, or both is less than 100° C.
 12. The method of claim 1, wherein the step of forming the first carbon layer comprises exposure of at least one precursor to a plasma having a radio frequency (RF) power of from about 50 W to about 300 W.
 13. The method of claim 1, wherein the step of forming the second carbon layer comprises exposure of at least one precursor to a plasma having a radio frequency (RF) power of from about 50 W to about 300 W.
 14. The method of claim 1, wherein the at least one additional layer comprises one or more silicon oxide layer(s), or one or more silicon nitride layer(s), or both.
 15. The method of claim 1, wherein the first carbon layer is formed using no plasma treatment or weak plasma treatment such that the carbon layer has high flowability and low etching selectivity.
 16. The method of claim 15, wherein the weak plasma treatment comprises plasma treatment with a radio frequency (RF) power of from about 50 W to about 300 W.
 17. The method of claim 15, wherein the weak plasma treatment comprises an exposure time to a plasma of from about 1.0 sec to about 10.0 sec.
 18. The method of claim 1, wherein the second carbon layer is formed using plasma treatment with a strong plasma treatment.
 19. The method of claim 18, wherein the strong plasma treatment comprises plasma treatment with a radio frequency (RF) power of from about 100 W to about 800 W.
 20. The method of claim 18, wherein the strong plasma treatment comprises an exposure time to a plasma of from about 5.0 sec to about 30.0 sec.
 21. The method of claim 1, wherein after the step of partially removing the second carbon layer, at least a portion of the second carbon layer remains within the recess.
 22. The method of claim 21, wherein the portion of the second carbon layer remaining within the recess has a top that is substantially coplanar with a surface defining a recess opening.
 23. The method of claim 1, wherein partially removing the first carbon layer, partially removing the second carbon layer, or both, comprise plasma etching with one or more of oxygen-containing gases, such as oxygen (O₂) or N₂O, or hydrogen-containing gases, such as hydrogen (H₂) or NH₃.
 24. A structure including high aspect ratio features fabricated by the method of claim
 1. 25. A system that performs the method of claim
 1. 